US2435412A - Plasticized natural resin material - Google Patents

Description

Patented Feb. 3, 1948 assure r ms'rrcrzan m'runsr. nasm m'ramsr.

Frank J. Soday, Swartbmore, Pm, assignor to The United Gal Improvement Company, a corporation of Pennsylvania u. Drawing. Application Ootober 22, me,

Serial No. new

110mm. (Cl-1H0) ducible softeni points and are compatible with drying oils, w e rubbers are not.

. It is the object of the present invention to provide new compositions of matter comprising high-boiling aromatic oil separated from pctroleum oil gas tar and one or more natural resins and/or resinous derivatives or natural resins. Another object of the invention is the provision of a high-boiling aromatic oil which is suitable for use alone or in combination with other substances as a softener or plasticizing agent for coating compositions containing one or more natural resin and/or resinous derivatives of natural resins. A further object of the invention is the provision of new molding compositions comprising a high-boiling aromatic oil in com- .bination witlrone or more natural resin and/or resinous derivatives of natural resins. Other objects and advantages of the invention will be apparent to those skilled in the art from the I following description.

A feature of the invention is the provision of adhesives, paper and textfle treating agents, leather treating agents, special inks, binders, coating and impregnating compositions, putties, sealing agents, and the like, comprising one or more natural resin and/or resinous derivatives of natural resins and an aromatic oil of the type described.

For convenience in description the natural resins and their resinous derivatives will be generally referred to herein as natural resin material unless it is desired to distinguish particularly a specific resin or class of resins within the broad group.

Other ingredients, such as waxes, rubber, both natural and synthetic elastomers in general, derivatives of rubber or elastomers, drying oils, pigments, extenders, fillers, organic dyes and coloring agents, driers, and solvents may be incorporated in compositions of the type described for specific applications. if desired.

While the use of certain aromatic hydrocarbons such as naphthalene, anthracene, and phenanthrene have been suggested for use as plasticizers for certain synthetic resins, such as polystyrene. the use of such aromatic hydrocarbons ,for this purpose has not met with general acceptance in the industry. This has been due mainly to the fact that such crystalline materials tend 'to volatilize or sublime from the surface of the resin orplastic with which they have been incorporated, thus impairing or destroying the transparency and/or finish of the article or object in question.

I have discovered that aromatic hydrocarbon oil boiling above 210 (1., said oil having been separated from tar produced during the production of gas by a process involving the pyrolytic decomposition of petroleum oil with or without the aid of catalysts. is unusually well adapted as a softening agent for natural resin material.

Such high-boiling aromatic oils are preferred,

which have a preponderant portion boiling above approximately 250 (2.; still more preferred are 'those having a preponderant portion boiling above approximately 275 0.; even more preferred are those having a preponderant portion boiling above approximately 300 0.; and especially preferred are those having a preponderant portion boiling above approximately 325 C. For certain purposes, it may be preferred to employ high-boiling aromatic oils of this type which boil substantially within certain ranges, for example, between 225 and 450. C., more preferably between 300 and 450 0., and still more preferably between 325 and 450' 0., though for other purposes relatively narrow cuts confined to the lower boiling ranges may be preferred.

The excellent results obtained when such aromatic oils are used as plasticizing and/or softening agents for natural resin material are due largely to the exceptional solubility and low volatility characteristics of such oils, as well as to their excellent compatibility with natural resin material generally. Their solubility characteristics are of particular value when preparing resin-plasticizer compositions of this type, largely reducing the time ordinarily required to prepare such blends.

In addition, the exceptionally low viscosity characteristics of aromatic oils of the type described greatly assists in the blending operations, and insures rapid and complete penetration.

Aromatic oils of the type described are exceptionally stable, and are strongly resistantffto decomposition, thus insuring the production of uniform compounds and finished articles free from decomposition products. Such compounds, and

3 the finished articles prepared therefrom, possess 2 very good aging characteristics.

Aromatic oils of the type described herein are extracted and/or distilled products, consequently they contain very little, if any, free carbon or other extraneous materials. This is of considerable importance from the standpoint of the preparation of clean, uniform resineplasticizer compositions.

It has been discovered that quantities of high-boiling aromatic oils of the at relatively high temperatures, such for exvery considerable type described are contained in the tar -pro- This is ample as in the manufacture of oil gas or car- 1 buretted water gas at average set temperatures above 1300" F. and at close to atmospheric pressures and also particularly so when the oil pyrolyzed is naphthenic, such as afcrude oil classifiable in classes 5 to 7 inclusive, according to the method of classification of the'Bureau of Mines or a fraction or fractions of such an oil.

Recently, methods have been developed for the recovery of unusually large quantities of arcmatic hydrocarbon boiling in the ranges set forth, from petroleum oil gas tar. produced in the manufacture of gas, such for example, as

3 carburetted water gas, oil gas, or the like. These methods recover high-boiling aromatic oils which 1 are unique in character.

procedures employed for the purpose of petroleum tar dehydration and fractionation have heavy polymers, which became inextricably mixed with the heavy black pitch constituents and with the higher-boiling non-heat polymerizable aromatic oils present. As a result, the

high-boiling non heat polymerizable aromatic oils were retained by the residual tar or pitch.-

In copending application Serial Number 370,-

608, filed December 18, 1940, by Edwin L. Hall and Howard R. Batchelder, which has matured into Patent 2,387,259, granted October 23, 1945,

the high-boiling aromatic'hydrocarbon oils containing heat polymerizable monomeric aromatic hydrocarbons boiling above 210 C. and separated from the heavy black pitch constituents of the petroleum tar are described and .claimed, to-

gether with heat polymers produced from said polymerizable oils. n

In copending application 386,232, filed April 1, 1941, by Waldo C. Ault, which has matured into Patent 2,387,237, granted October 23, 1945, there is described and claimed the production of catalytic resins from the heat polymerizable and/or catalytically polymerizable monomeric hydrocarbons boiling above 210 C. and separa'ted in monomeric form from the heavy black pitch constituents of the petroleum tar.

The high-boiling aromatic oils of the type described may be isolated from the resins obtained from each of these processes.

In the manufacture of oil gas and carburetted The usual distillation. I

been such as to polymerize the readily heat polysmerizable monomers boiling above 210 C., which are frequently present in large proportions, into tion of the hydrocarbon constituents of residual tar,

matic hydrocarbons and heat polymerizable unsaturated monomeric aromatic hydrocarbons boiling above210 C.

In copending application 353,034, filed August '17, 1940, by Howard R. Batchelder, which has matured into Patent 2,383,362, granted August 21,1945, there is described the dehydration "of such petroleum taremulsio s \and the fractionaonstituents thereof with therecovery of monomeri unsaturated heat polymerizable hydrocarbon con tituents and aromatic oils separate from the 11 avy black pitch y the solvent extraction of the emulsion with hydrocarbon solvent suchyas liquefied propane or butane.

Other processes, forexample fractional condensation, might be employed to recover these high boiling aromatic hydrocarbons separate from the heavy black pitch constituents of the tar. Also processes for oil pyrolysis which avoid the formation of emulsions, may be employed for the production of the high-boiling aromatic hydrocarbons. Furthermore, while it may be preferred to employ petroleum.oils or cuts therefrom, which are classifiable in classes 5 to 7 inclusive according to the method of classification of the Bureau of Mines, and particularly in class 7, other oils may be employed. A

As a result of separation of the light oil and higher-boiling aromatic oil components of the products of such petroleum oil pyrolysis from the residual tar, without polymerization or with materially reduced polymerization, a substantially pitch-free highly aromatic hydrocarbon'material in the range of from'210 to 450 may be separated having a portion boiling with- C., or higher, which may contain from 5% by any desired method, such as by distillation,

which may be assisted by steam and carried out under reduced pressures.

Polymerization may be effected by heating the 1 total material separated from the residual tar sufi'iciently to polymerize the readily heat polymerizable monomers boiling within the range of from 210 to 450 0., but insumcientlty to appreciably polymerize the heat polymerizable material water gas, the tar produced is usually in the form of an emulsion .due to the condensation of u; 9.

contained in lower boiling ranges, such, for instance, as methylstyrenes and styrene. This may be accomplished, for example, by heating with stirring for 4 hours at 200 0., followed by distillation under vacuum to isolate the resin. The higher-boiling aromatic oils then may be separated by fractional distillation.

It may be preferable, however, to first effect separation by fractional distillation between to 30%, and higher, of monomeric unsaturated aromatic-hydrocarlight all boiling below say 210' c. and oils boiling above say 210' C.

light oil from the higher-boiling oil, may then be removed by distillation under vacuum.

As hereinbefore stated, after polymerization the high-boiling aromatic oils may be isolated from the resin by distillation in vacuum, which may be assisted by steam.

The high boiling polymerizable monomeric material derived from tar obtained in the pyrolysis of petroleum, by rapid distillation or solvent extraction methods also may be polymerized prior to the separation of the desired high-boiling aromatic oils by the application of certain catalysts, either with or without the simultaneous, or otherwise, application of hea'tyfor example as described and claimed in the above copending application, Serial No. 386,232, filed April 1, 1941, by Waldo C. Ault.

Catalysts such as mineral acids, fo example, sulfuric acid, hydrogen chloride, acids of phosphorus, or acid-acting metallic halides or complexes of said halides, preferably organic solvent complexes, as for example, borin trifluoride, aluminum chloride, boron trifluoride-dieth yl ether complex, boron trifluoride-dimethyl ether complex, boro'n trifluoride-phenyl ether complex, boron trifluoride-phenyl methyl ether complex, boron trifluoride-dioxan complex, boron trifluoride-toluene complex, corresponding aluminum chloride complexes, and the like, may be employed for this purpose.

The metallic halides and their complexes employed are characterized by their ability to hydrolyze in the presence of water to give an acid reaction and, hence, for convenience they may be termed acid-acting metallic halides.

While high-boiling oils of the type described may be isolated from the tar emulsion by either distillation or solvent extraction methods, as

- difiiculties.

The processes, which minimize or avoid polymerization in the separation of the high-boiling aromatic oil from the tar, thus produce. highboiling aromatic oils which difier from those produced by conventional processes not only in their v content of high-boiling heat polymerizable unsaturates, but also in their content of the higherboiling non-heat polymerizable aromatic constituents. The high-boiling aromatic oils produced by these methods are therefore unique.

In connection with the isolation of these highboiling aromatic oils by the preterred method, nameLv, by the solvent extraction of the tar emulsion, it should be .emphasized that the mixture of aromatic oils'and unsaturated oils obtained by such methods may be fractlonally dis tilled prior to, during. or after polymerization to isolate the aromatic oils having the desired highboiling range. Separation by distillation prior to polymerization may be preferred in certain cases for reasons more particularly set forth in said copending applications.

Thus, the extracted oils may be distilled prior to polymerization to give a fraction boiling above, say for example 275300 C., and 'a lower boiling fraction. These may be polymerized separately, after which the high-boiling aromatic oils of the type desired may be isolated from the resinous materials obtained.

Theprocess may be further illustrated by the following examples.

Example 1 Petroleum oil gas tar emulsion obtained by the pyrolysis of a Bureau of Mines type 7 naphpointed out previously, I prefer to employ highboiling oils which have been isolated by solvent extraction methods because of the presence therein of very much larger proportions of highboiling aromatic oils of the type desired. The flash-distillation method of isolating such oils from the tar emulsion may permit the polymerization of a portion of the unsaturated materials to take place, though very greatly ,less than when using conventional methods, thus increasing the quantity of resinous and/or pitch-like materials present. The presence of these polymers reduces the quantity of the aromatic oils, and particularly those having the higher boiling ranges, which may be isolated from the residual tar or pitch.

While aromatic oils boiling above 210 0. may

be produced by conventional methods of distillation of the products of vapor phase oil pyrolysis produced in the manufacture of gas, and may be employed in accordance with the present invention, such aromatic oils are by no means as preferred for this purpose, as are the high-boiling aromatic oils produced by the use of separation methods, which minimize polymerization of the high-boiling heat polymerizable unsaturates.

In conventional distillation methods, the tars are subjected to elevated temperatures for such thenic oil in the presence of steam in. a ceramic chamber at temperatures above 1300 F. is 'extracted with liquid propane. After removal of the propane, the extracted oil is flush distilled to give a fraction boiling almost entirely above 250 C.

This fraction is polymerized by heating to a temperature of 200 C. for a period of 4 hours after which the aromatic oils are isolated by distillation until a vapor temperature of approximately 200 0., or higher, is reached at sure of 20 mm. of mercury, absolute.

- Example 2 8. pres- A sample of extracted and distilled oil similar to that employed in Example 1 is polymerized by the addition of 96% sulfuric acid in small portions at temperatures below 50 C. until no further temperature rise is noted. .The addition of 1% by weight of acid usually is sufllcient to insure com plete polymerization.

The acid sludge, layer then is removed, either with or without the addition of naphtha to reduce the viscosity of the mixture, and the polymerized material washed and neutralized. The

. high-boiling'aromatic oils then are isolated by distillation under reduced pressure.

/ Example 3 A sample of extracted and distilled oil similar to that employed in Example 1 is polymerized by the addition of 3% by weight of aluminum chloridc-diethyl ether complex at temperatures below lengths of time as to polymerize the far greater 1 5 C. A t the P m i n ha n mplated, the catalyst is neutralized-by the addition of an aqueousaliraline solution. brother desired filter aid then is'added andthe mass fil tered. The filtered material is-distilled under reduced rpressurestto isolate the high boilin'g w i unatic-oils.

Any combination ofthe foregoing or other 'methods may, of course,'b employed the high-boiling aromatic oils.

The-oils obtained maybe employed in'natural resin material. compounds" or; blends without furbyany desired method. i 1

Th s. the high-boilingaromatic oilsi riiay" be if de'siledtthey may be rurtii r 'rennen oli 'tl'eatedi renne'd bywashing-withtone orrnorevportions of i sulfuric acid,- preferably of 96%concentration,

isolate a 1 thertreatment with exeelieirtreaiiits. However.

further distilled and/or, fractionated, oritmay until all. or substantially all, of'thecoloredbodies are removed. The oil then maybe-contacted with clay orother surface-active agents, if desired, to

removeany remaining impurities. Oils ranging o'ftheoil obtained depending, among other things,

,upon" theseverity of the'reflningoperation em ployed.

;in color froma light yellow to water white are readily obtained in this manner, the exact color Other refining methods may, of course, be employed if desired, elther aloneror in conjunction with acid washing, or otherwise. Thus,.the hieh-v boiling aromatic oils may becontacted with, or percolated through, activated clay or other surface active agent. t

I have discovered that aromatic oils of the type described herein should preferab have thepreponderant part thereof boil above at least 250 6.,

softener and/or plasticizing agent for 'iiatuni resin material may be isolated. from the tire: .tar'emulsion obtained as ares'ult'of .thepyrglytic decomposition ofpetroleum, orxa fraction thereof. by the distillatlon'or. more'preferably the solvent extractionof the=tar orv tar, emulsion. '-;The extract obtained may beseparated intoa high-boiling and e loweb'o'iling fractionpif'de-e r sired, afterQwhich the high-boiling fraction, or

the overall extract, may be subjected to, polymerization to remove the unsaturatedmaterials present. The oil obtained'fromsu'ch operations .'then may be'retlned, such as by sulfuric acid washing and/or other refining voperations,after which the oil maybe usedas such,- or-it maybe be processed otherwise. 7

The oil obtained from the polymerizing operation, after separation.of -therpolymers, also'may suclr'funrefined oil may be'fractionated priorto use, if desired.

The on obtained'frcm the polymerizing operation also may be treated with clay or other surface active agent, ieitherTbefore-or afterlseparation'ifrom thefipolymers', followed by filtration and/or distillation, if desired. Successive .cl'ay treatments may be employed.

The mixture of oil and resin obtained from the polymerizing operation alsomaybe used as such for the preparation of natural resin materialcompositions, and such mixture may be reflnedsuch and more particularly above at least 275 0., in

order-to insure the production of.natural resin.

material compositions having unusually desirable properties. Excellent results are obtained when aromatic oils of the type described having the preponderant part thereof boiling above at least 300-C., more particularly above 325 C. and still more particularly above 340 C., are employed.

In addition, such oils are preferredwhich have mixed aniline points below 15 C.,-and more particularly below 10 C. A mixed aniline point of a.

givenoil is defined as the critical solution tem; perature of a mixture of 10 cc. of anhydrous aniline, cc. of the oil being tested, and 5 cc. of a naphtha having a straight aniline point 'of 60 C.

Excellent results have been obtained employing high-boiling aromatic oil produced under such conditions of oil pyrolysis and under such conditions of separation from the resulting petroleum oil gas tar, that the material boiling-above 210 0.,

ents of the tar, contained at least 5%. and preferably at least and still more preferably at least or higher of heat polymerizable unsaturates. g

As pointed .out previously, high-boiling aromatic oils of the type described which have been found to be particularly adapted for use as a as by clay contacting prior to'us'elif desired.

The oil separated from the tar or taremulsion by flash distillation or preferably by solvent extraction methods followed by distillation to separated materials boiling below 250 .C. or, more particularly, below 275 C., or still more particularly below 300 C., if desired, and containing higher-boiling aromatic hydrocarbons and unpolymerized or artially polymerized unsaturated aromatic hydrocarbons; may be used as such for the preparationofjnatural resin material compositions, r it may be refined by any desired method such as, claycontacting-prior to use.

As the unpolymerized aromatic material present in such-mixture'is extremely heat sensitive, practically all of the unsaturated aromatichydrocarbons present may be, if desired, converted to resinous polymers during the mixing, blending, or other operations incident to the preparation of the natural resin material composition.

Accordingly; the mixture of aromatic-hydrocarbons including'unsaturated aromatic hydrocarbons obtained from the tar; or tar emulsion by flash distillation or preferably by solvent ex traction methods, followedby distillation maybe us'edas such fort'he preparation ,of compositions .of the type described herein, provided preferably however that. the preponderate portion thereof boils above 250 C., orsuch mixture may be perwhen and as separated from the pitch constitu- I tially or completely polymerized prior to use. The partially or completely polymerized mixture also may be distilled to remove a part or all of the resinous polymer, after which the distillate may be distilled and/or refined if desired prior to use.

The invention in its broad aspect, therefore, includes the employment of a-high-boiling aromatic oil of petroleum oil gas tar origin of'the type described as an ingredient in natural resin.

material compositions either in admixture or not with unsaturated aromatic hydrocarbons boiling in the same or neighboring boiling rangesand/or resinous polymers derived from such unsaturated aromatic hydrocarbons,

aioaua anac; natural resin derivatives such as hardened resins and run resins of the above varieties and others, esters of resins of the above varieties and others such as rosin esters including ester gum, esters of copal, dammar, pontianao, kauri, sandarac, elemi, shellac, chicle, amber and others;

hydrogenated esters of the above various natural resins and others; chlorinated natural resins of the above varieties and others, especially if compatible with cellulose derivatives such as cellulose acetate.

Esters may be prepared by esterification of individual natural resins or mixed resins. Hardening and running may be carried out before or after esterification, or otherwise, and may be carried out with mixed resins or resin esters.

The various natural resins may be esterifled according to known methods with polyhydric alcohols, such as glycerol, polyglycerol, glycols, with aliphatic monohydric alcohols, with phenols and naphthols and with high boiling esters to bring about interchange of groups between the resin acid and the ester and otherwise.

The esteriflcation may if desired be carried out in the presence of a drying oil such as linseed oil or tung oil.

Running may be accomplished in any desired manner, such as by heatin in a suitable container until the desired degree of oil compatibility, or other desired characteristics, have been imparted to the resin or mixture of resins.

In general, aromatic oils of the type described are added to natural resin materials to (1) improve their flexibility, (2) reduce their softening point, (3) reduce their viscosity, (4) improve their workin roperties, and/or (5) impart tackiness and improve the adhesive properties of the resin.

Other plasticizln agents may be used incon- Junction with aromatic oils of the type described herein.

However, I generally prefer to employ aromatic oils of the type described herein alone as plasticizing agents for natural resin material. When one or more secondary plasticizing agents are employed in conjunction with aromatic oils of the type described herein in the preparation of resin-plasticizer compositions, I prefer to have the said aromatic oils as the preponderating constituent of such mixture of plasticizing agents.

It should be emphasized that aromatic oils of the type described herein may not be compatible with certain natural resin materials in all proportions. Consequently, care preferably should be exercised in using a given resin in order not to exceed the compatibility limits of the respective components if a clear coating film, or a mix ture, is desired. In case a non-homogeneous mixture is obtained, the addition of a secondary plasticizing agent more completely soluble in both the resin and the aromatic oil usually will be found to result in the formation of a completely homogeneous mixture. The use of a third component, other than a plasticizing agent, as a solubilizin agent will be found to be advantageous in certain cases.

In certain cases, also, an opaque film or coating is not detrimental and may even be desired.

10 In such cases, the use of aromatic oils of the type described in proportions above the compatibility limits is indicated. "fir It is apparent, therefore, that a proper choice of the type of resin. and the ratio of resin to aromatic oil will enable one skilled in the art to prepare compositions possessing desired flexibility, softening point, viscosity, consistency, tackiness, and adhesiveness at will.

While any desired ratio of natural resin material to aromatic oil'may be employed, for many applications, I prefer to have the resin comprise at least oi the resin-plasticizer mixture, although larger proportions of aromatic oil may be employed in certain applications such as, for example, in the preparation of adhesives.

Excellent results may be obtained in many cases where the resin comprises at least of the resin-aromatic oil mixture.

In certain other cases such as for example in the preparation of rosin ester-aromatic oilcompositions, preparations containing aromatic oil of the type described herein in excess of 50% such as from 50% to 70% (for example, 60%) may be employed to impart unusual tacky characteristics.

It is to be understood, of course,'that varying quantities of aromatic oils of the type described may be employed, the quantity used, in general, depending largely upon the result desired. Thus the use of relatively large quantities of aromatic oil will increase the flexibility and extensibility of a given resin substantially while at the same time reducing its softening point somewhat.

The aromatic oil and resin may be compounded in any desired manner, such as by (1) mixing the molten resin and the aromatic oil, (2) the use of a mutual solvent, and (3) compounding at room or elevated temperature in the absence of, a solvent by the use of a two-roll mill, a Banbury mixer, or otherwise. Any combination of the foregoing methods also may be employed, if desired.

In hot-melt mixing, I generally prefer to melt the resin and add the aromatic oil to the molten resin with good agitation. Other procedures may of course, be employed.

In case a solvent is incorporated in the resinaromatic oil mixture, one which is capable of forming a clear solution preferably is chosen? However, in certain cases it may be desired to add only a suiiflcient quantity of solvent to reduce the melting point of the mixture, or to form a paste of varying consistency, in which case the degree of solubility of the resin and/or aromatic oil in thesolvent is of less importance.

Suitable solvents may be selected from the hydrocarbons or from hydrocarbon fractions, such as benzene, toluene, xylene, solvent naphtha,

mineral spirits, V. M. 8: P. naphtha, hydrogenated hydrocarbon solvents, and the like, chlorinated solvents, such as ethylene dichloride,

chloroform, and carbon tetrachloride, and miscellaneous organic solvents, such as esters and ketones. As many of the resins are quite soluble in aromatic solvents, such solvents are preferred for the preparation of resin-aromatic oil solutions to be used in certain specific applicaalso maybe 1i poratingrubber, either natural or artificial, or derivatives or modifications thereof, in such compositions. Examples of such materials are natu- -ral rubber, such as raw plantation crepe, latex,

and the like; reclaimed rubber; synthetic rubbers or elastomers, such as those obtained by the polymerization of butadiene; or other diolefines, either alone or in admixture, or the copolymer ization of one or more dioleflnes with one or more unsaturated or reactive materials, suchas styrene. methyl styrene, acrylic nitrile, isobutylene, and the like, or by the polymerization of one or more substituted dioleflnes, such as 2- chloro-butadiene-l,3, either alone or in admixture with other unsaturated'and/or reactive materials, and other synthetic elastorners; substituted and/or modified natural and/or synthetic rubbers, such as chlorinated rubber; olefin-poly sulfide typerubbers; resinifled rubber, factice; and the like.

While rubber or rubber-like materials may be added to natural resin materiabaromatic oil compositions in the solid state, I generally prefer to incorporate a solution of one or more of the ingredients with the remaining ingredients. An alternative method comprises blending solutions of the various components.

Rubber also may be added to the resin-aromatic oil composition, in solid form or in the form of a solution, for example in the form oi! a rubber cement, which generally comprises a solution of rubber in a suitable solvent, which may contain other ingredients.

The field of utilization of natural resin mate rial-aromatic oil compositions also may be enlarged substantially by the incorporation therein of one or more drying oils.

Examples u such oils are linseed oil, tung oil, oiticica oil, p 'illa oil, soya bean oil, cashew nut oil, fish oil, nienhade'n oil, sardine oil, synthetic and/or modified drying oils, and the like. Such drying oils may be bodied prior to, during, or after the addition of the resin-aromatic oil composition. In addition, one or more of the ingredients, such as the resin, may be incorporated in the drying oil or bodied drying oil, prior to the addition of the other ingredient, or ingredients.

In case a drying oil is; incorporated in the resin-aromatic oil composition, driers may be added if desired in order to assist in hardening the drying oil after application. Examples of suitable driei's are the lead, cobalt, and manganese salts of high molecular weight organic acids, such as rosin acid or naphthenic acids. Litharge or other drying agents, such as japan driers, also may be employed.

Natural resin material-aromatic oil-drying oil compositions may be prepared and used without further modification, although other ingredients incorporated therein, such as solvents.

Both rubber and drying oils may be incorporated in natural resin material-aromatic oil compositions for use in certain specialized applications. In general, it may be said that rubber improves the adhesive properties or the mixture, while the drying oil improves the mechanical strength and solvent resistance of the composition after applications.

As both rubber and drying oils generally are not compatible in all proportions with certain of the natural resins and natural resinderivatives of the type more particularly described herein, care should be exercised not to exceed 76 assure such compatibility limits it a clear composition is desired.

Other-material which may be incorporated in the natural resin material-aromatic oil compositions are cellulose derivative plastics such for example as organic esters of cellulose, such as cellulose formate, cellulose acetate, cellulose triacetatc, cellulose propionate, cellulose butyrate, cellulose benzoate, and the like; mixed organic esters of'cellulose, such as cellulose acetopropionate, cellulose acetobutyrate, cellulose propionate butyrate, and the like; inorganic esters of cellulose, such as cellulose nitrate; mixed organic-inorganic esters of cellulose, such as cellulose mtro-acetate; cellulose ethers, such as methyl cellulose, ethyl cellulose, benzyl cellulose,

and the like; mixed cellulose ethers, such as methyl ethyl cellulose; mixed cellulose estermium yellow, zinc yellow, iron yellow, ochre, umi mineral wool, rock wool, and the like.

others, such as ethyl cellulose acetate, oxyethyl cellulose acetate, and the like; other cellulosic derivatives, such as hydroxypropyicellulose triacetate; and mixtures of the foregoing.

As indicated previously, other ingredients may be added to the resin-aromatic oil composition, either alone, or in combination, or in conjunction with the addition of rubber and/or drying oil. Examples of such additives are pigments, fillers, extenders, organic dyes, antioxidants, antiskinning agents, and the like.

Suitablepigments include red lead, vermilion, cadmium red, Venetian red, chrome yellow, cadber, ultramarine blue, iron blue, emerald green,

chrome green, titanium dioxide, carbon black,-' I

lampblack, iron oxide black, manganese black, lithopone, white lead, zinc white, various metallic pigments such as aluminum and bronze powders,

and the like. a 7

Examples of fillers and'extenders are whiting, barytes, kaolin, blanc fixe, gloss white, asbestos,

Organic colors which may be-employed as additives include basic dyes such as methyl violet, Victoria blue, malachite green, brilliant green, magenta, thioflavine, auramine, and the like; acid dyes such as sulfonic or carboxylic acid derivatives or color bases: mordant dyes; and pigment dyes such as azo dyes, vat dyes, and phthalocyanine compounds.

Examples of antiskinning agents and antioxidants are dipentene, catechol, hydroquinone, and secondary aryl amines, such as phenyl alpha naphthylamine. In general, antiskinning agents and antioxidants are used only when drying oils have been incorporated in the resin-aromatic oils composition.

.Waxes also may be incorporated in natural resin material-aromatic oil compositions of the type described herein, of which paraffin may be considered to be the most important. Examples of other waxes and waxy materials which may be blended with resin-aromatic oil compositions of the type herein disclosed are bayberry wax, ozokerite, Rilan wax, spermaceti, stearic acid, lanette wax, lanolin, montan wax, Japan wax, cetyl alcohol, esters of cetyl alcohol, ceresin, candelilla wax, carnauba wax, beeswax, sugar cane wax,

assume Natural resin material-aromatic oil compositions of the type described herein are well adapted for use in a large number of industrial applications, due principally to the unique properties of the high-boiling aromatic oils employed in their preparation. Thus, such compositions may be used (1) to treat, coat, and/or impregnate fibrous materials in general, such as paper and textiles, (2) to waterproof, impregnate and/or finish leather, either natural or artificial, (3) as adhesives and binding agents, (4) to form putties, caulking agents, and sealing compounds, (5) as film forming compositions, (6) for the preparation of inks, (7) for the preparation of both hot and cold molding compositions, and (8) for the preparation of resinous and/or plastic blocks, sheets, rods, tubes, foil, filament, molding compositions and the like.

Modifying agents may be incorporated in the resin-aromatic oil compositions which are to be used for any desired application, if desired. Thus, for example, resin-aromatic oil compositions which are to be used to coat and/or impregnate fibrous materials may contain rubber, drying oils, solvents, and/or waxes.

- Resin-aromatic oil compositions of the type described herein, either alone or in conjunction with certain modifying agents, are excellent waterproofing, coating, impregnating, and/or finishing agents for a wide variety of fibrous materials. Thus, for example, such compositions may be used to coat and/or impregnate felts to be used as floor, wall, or roof coverings. Such compositions frequently contain one or more pigments, coloring agents, fillers, and/or extenders.

Natural resin material-aromatic oil composi: tions employed to water-proof, impregnate, and/or finish leather may contain one or more waxes, and may contain solvents, pigments, and/or coloring agents.

Natural resin material-aromatic oil compositions may. be employed as adhesives or binders without the addition of any modifying agents. Such adhesives usually are of the hot-melt type,

that is, the resin-aromatic oil composition is' softened or melted by the application ofheat prior to or during its application to the surfaces to be joined.

Solvents also may be incorporated in such compositions, if desired.

The use of resin-aromatic oil compositions of the type described herein for such adhesive purposes will be found to be unusually satisfactory due mainly to the unique characteristics of the aromatic oil employed. Such compositions may be used in the fabrication of cardboard. to join paper or cardboard to form containers or other objects, for the preparation of laminated objects or units, such as laminated wood, and the like.

Such compositions will be found to be particularly useful in the fabrication of cardboard containers formed by rolling a sheet of kraft, or other, paper over a cylindrical form, the adhesive being applied continuously, or otherwise, to unite the continuous, or other, plies to form a container of the desired size and rigidity. Due to the excellent waterproofing qualities of the adhesive. the container obtained usually requires no further waterproofing, thus eliminating one operation in the manufacture of containers which are to be used for outdoor applications.

-In addition, resin-aromatic oil compositions of l the type described herein also may contain fillers,

such as starch, asbestos, and the like, rubber, pigments, coloring agents, solvents, and similar materials. Special adhesives for specific applications may be formulated by the addition of one or more of such modifying ingredients to resinaromatic oil compositions of the type described herein. I

Natural resin material-aromatic oil compositions prepared from aromatic oils of the type described herein also find wide application in the formulation of putties, caulking agents, and sealing compounds. Putties and caulking compounds also frequently contain drying oils, fillers such as clay, bentonite, kaolin, asbestos, and the like, pigments, organic coloring agents, solvents, and similar materials.

Sealing compounds frequently contain drying oils, rubber. fillers. pigments, and the like, in addition to the resin and aromatic oil.

Resin-aror natic compositions of the type described herein are particularly well adapted for 'use as film forming compositions to coat a wide variety of surfaces, such as those of wood, metal,-

fibrous materials, ceramic materials, such as concrete, brick, stone, stucco, and plaster, and the like. Such compositions frequently are employed in the absence of any modifying agent, being applied in a softened or molten condition to the surface to be coated.

Thus, a composition comprising a natural resin material and an aromatic oil of the type described herein, may be softened or melted by the appli-' cation of heat, after which it may be applied, such as by. dipping, brushing, or spraying, to the surface of metallic objects, particularly those of iron or steel, to form a protective layer thereon.

Pigments or fillers may be incorporated in resinaromatic oil coating compositions of the type disclosed herein, as well as solvents, drying oils, organic,coloring agents, and the like. Sufficient pigments and fibers, such as asbestos, may be added to give composition possessing a definite fibrous structure. Such compositions usually are applied by means of a trowel, or by similar methods. I,

Compositions comprising an aromatic oil of the type described herein. a natural resin material and a drying oil, preferably bodied, find numerous applications in the coating industry. Such compositions may contain a solvent, preferably one of a hydrocarbon nature.

Resin-aromatic oil compositions of the type disclosed herein are excellent ink bases. Pigments and/orcoloring agents usually are added, such as lampblack. Venetian red. chrome yellow, and the like. Drying oils may be incorporated in such inks and they may contain solvents, particularly those of a hydrocarbon type.

The herein-disclosed resin-aromatic oil compositions also are well adapted for use in both hot and cold molding compositions. The cold molding compositions usually contain a filler, such as asbestos, and a solvent, particularly a hydrocarbon solvent, and may contain one or more dryin oils, pigments, organic coloring agents, and the like. o

Other applications for resin-aromatic compositions of the type disclosed herein will. of course. suggest themselves to persons familiar with the art upon an inspection oi the foregoing disclosure.

Aromatic hydrocarbon oils of the type described because of their unusually high solvent power are particularly outstanding in their ability to disperse other additives. Their low surface tension promotes unusual wetting power, which in turn. 'greatly adds rapid dispersion. Thusiboth relatively high solvent power and relatively high dispersion power combine to make aromatic oils of the type described singular and unique.

These properties are of greatest importance in plasticizing and compounding operations insuring not only the desired dispersion of the arematic oil itself and any other-additive, but also such dispersion in a relatively short time and in incorporated in natural resin materialat a considerably higher rate under the same-conditions andiat a pronouncedly higher rate. This greatly increases the throughput of any given manufacturing unit.

Generally speaking, lower viscosities for the same amount of material used may be obtained when using my aromatic oils. This is of outstanding importance in the formulation of cements and of coating compositions, for example, for the coating of fabrics forthe same viscosity as higher content of solids or, in other words, of resins.

On the other hand, when it is desired to impart to the resin product hard, horny and tough characteristics this may be accomplished by employing my aromatic oil in combination with resin polymerized therein or by the addition of resins of other types such as, for example, a coumaronindene resin.

An advantage in using resins which may be polymerized in the oil itself is that-they possess a very high compatibility with other resins and particularly with natural resin material.

Certain of the foregoing outstanding properties of my aromatic oil are demonstrated'in the following examples.

Example '4 satisfactory waterproof finish is obtained.

Example'5 Upon applying a resin-aromatic oil composition -.of the type described in Exampled to a number of piles of paper in a molten condition, and uniting the plies under pressure, a laminated block of paper is secured.

Example 6 a A: mixture of 40 parts of hydrogenated rosin,

20 parts of bodied linseed oil, 10 parts of an aromatic oil of the type described herein and boiling above 250 C., and 30 parts of kaolin is thoroughly blended. The composition is satisfactory for use as a putty, caulking, or sealing agent.

alarm:

laamplc 7 Upon heating a composition of the type described in Example 4 and dipping a section of steel pipe in the molten composition, a satisfactory mill coating is formed thereon.

Example 8 described herein and boiling above 250 C.

Example 9 A cold molding composition may be prepared by thoroughly mixing'a blend containing 20 partsof a rosin ester, 10 parts of an aromatic oil of the type described herein and .boiling above 300 C., 10 parts of bodied linseed oil, 10 parts of a hydrocarbon solvent, and 50 parts of as bestos, followed by aging the mixture until the desired degree of plasticity is secured, subdividing and screening.

The molding composition may be subsequently molded and baked.

As previously pointed out, the unusually good properties possessed by natural resin materialaromatic oil compositions prepared from aromatic oils of the type disclosed herein are largely due to the unique properties of such aromatic oils. Among these desirable properties may be mentioned (1) their relatively low free carbon content and their comparative freedom from extraneous materials, (2) their excellent solubility and compatibility characteristics, (3) their relatively low viscosity-and viscosity-imparting characteristics, and (4) their stability.

My natural resin material-aromatic oil compositions are particularly well adapted for the coating and/or impregnation of organic fibrous materials in general including vegetable and animal fibers such as hair, leather and the like.

For convenience in the claims the term fabric" is used generically to include a woven, felted, knitted or other similarly fabricated material as well as the material used'in its making such as organic fibers and threads. Thus, for example, paper is a fabric prepared by felting paper-making fibers. Textile fabrics are prepared by weaving or knitting. A thread is a fabric made'by spinning or twisting fibers, yarns and filaments.

In the specification andin the claims, the term aromatic o unless otherwise modified, is intended to include the unrefined or refined oil separated from tar formed during the production of combustible gas by processes involving the pyrolytic decompositionof petroleum oil with or without the aid of catalysts, as well as mixtures of such aromatic oil with the unsaturated aromatic hydrocarbons derived from the same source and/or the resinous polymers derived natural resin or resinous natural resin derivative.

While various procedures and formulas have been particularly described these are of course subject to considerable variation. Therefore, it

will be understood that the foregoing specific examples are given by way of illustration, and that changes, omissions, additions, substitutions and/or modifications might be made within the scope of the claims without departing from the spirit of the invention, which is intended to be limited only as required by the prior art.

I claim:

1. A new composition of matter comprising one of a group consisting of natural resins, esters of natural resins and hydrogenated esters of natural resins and as a plasticlzer for said resin in aromatic oil having an aromatic hydrocarbon content of at least 95% and boiling above 210 C., said oil containing a plurality of oily aromatic hydrocarbons and having been physically separated from other components including pitch components of petroleum tar produced in the vapor phase pyrolysis at average temperatures above 1300 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

2. A new composition of matter comprising one of a group consisting of natural resins, esters of natural resins and hydrogenated esters of natural resins and as a plasticizer for said resin an aromatic oil having an aromatic hydrocarbon content of at least 95% and boiling above 250 C., said oil containing a plurality of oily aromatic hydrocarbons and having been physically separated from other components including pitch components of petroleum tar, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300 F. of naphthenic petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

3. A new composition of matter comprising one of a group consisting of natural resins, esters of natural resins and hydrogenated esters of natural resins and as a plasticizer for said resin an arcmatic oil having an aromatic hydrocarbon content of at least 97% and boiling between 325 C. and 450 C., said oil containing a plurality of oily aromatic hydrocarbons and having been physically separated from other components including pitch components or petroleum tar emulsion produced in the vapor phase pyrolysis at average temperatures above 1300 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic 011 being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

4. A new composition of matter comprising a natural resin and as a plasticizer for said resin' an aromatic oil having an aromatic hydrocarbon content of at least 95% and a density of at least 0.95 and boiling above 250 C., said oil containing a plurality of oily aromatic hydrocarbons and having been physically separated from other components of petroleum oil gas tar including pitch components thereof. said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 7 to 30% of the other.

5. A new composition of matter comprising an ester of a natural resin and as a plasticizer for said resin ester an aromatic oil having an aromatic 18 hydrocarbon content of at least 95% and having a density of at least 0.95 and boiling above 250 C., said oil containing a plurality of oily aromatic hydrocarbons and having been physically separated from other components of petroleum oil gas tar including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

6. A new composition of matter comprising rosin ester and as a plasticizer for the said rosin ester an aromatic oil'containlng a plurality of oily aromatic hydrocarbons and boiling above 250 C., said oil having an aromatic hydrocarbon content of at least 97% and having a density of at least 0.98 said oil having been physically separated from other components of petroleum oil gas tar including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

7. A new composition of matter comprising ester gum and as a plasticizer [or the said ester gum an aromatic oil containing. a plurality of oily aromatic hydrocarbon and boiling above 275 C., said 011 having an aromatic hydrocarbon content of at least 97% and having a density of at least 0.98 and having been physically separated from other components of petroleum oil gas tar including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300- F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to of one and 70% to 30% of the other.

8. A new composition of matter comprising a fossil natural resin and as a plasticizer for the said resin an aromatic oil containing a plurality of oily aromatic hydrocarbons and boiling above 250 C., said oil having an aromatic hydrocarbon content of at least 97% and having a density of at least 0.98 and having been physically separated from other components of petroleum oil gas tar including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1500 F. of petroleum oil in the production of combustible gas, in the composition the resin and aromatic oil being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

9. A new composition of matter comprising a kauri resin and as a plasticizer for the said resin .and aromatic oil cdnt'tining a plurality of oily least 0.98 and having been physically separated from other components of petroleum oil gas tar including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1300 F. of

petroleum oil in the production of combustiblegas, in the composition the resin and aromatic 011 being included in the reciprocal proportion of 30% to 70% of one and 70% to 30%01 the other.

10. A new composition of matter comprising a hydrogenated ester of a natural resin and as a plasticizer for said hydrogenated resin ester an aromatic oil containing a plurality of oily aromatic hydrocarbons and boiling above 250 C.,

said oil having an aromatic hydrocarbon con-, tent of at least 95% and having a density of at least 0.95 and having been physically separated from other components of petroleum oil gas tar;

including pitch components thereof, said tar having been produced in the vapor phase pyrolysis at average temperatures above 1800 F. of petroleum oil in the production of combustible gas, in

the composition the resin and aromatic oil "being included in the reciprocal proportions of 30% to 70% of one and 70% to 30% of the other.

11. A new composition of matter comprising;

one of a group consisting of natural resins, esters of natural resins and hydrogenated esters of natural resins, a drying oil, and as a plasticizer for said resin an aromatic oil containing a plurality of oily aromatic hydrocarbons and boiling above 275 C., said aromatic oil having an aromatic hydrocarbon content of at least 97% and v UNITED STATES PATENTS Number \Name I 7 Date' 2,217,988 Dawson Oct. 15, 1940 2,150,641 Thomas Mar. 14, 1939 -Gentzsch May 5, 1896 having been separated from other constituents of petroleum oil gas tar including pitch constituents thereof, said tar having been produced in the vapor phase pyrolysis at temperatures REFERENCES CITED The following references are of record in the 1 file of this patent: I

' OTHER REFERENCES Vapor Phase Cracking, Groil, Industrial and Engineering Chemistry, vol. 25, No. 7, July 1933, page 797.